Structural Characterization of 6-Halo-6-Deoxycelluloses by Direct-Dissolution Solution-State NMR Spectroscopy.

Regioselective modifications of cellulose using activated cellulose derivatives such as 6-halo-6-deoxycelluloses provide a convenient approach for developing sustainable products with properties tailored to specific applications. However, maintaining precise regiochemical control of substituent distribution in 6-halo-6-deoxycelluloses is challenging due to their insolubility in most common solvents and the resulting difficulties in precise structure elucidation by modern instrumental analytical techniques. Herein, an accessible NMR-based approach toward detailed characterization of 6-halo-6-deoxycelluloses, including the determination of the degrees of substitution at carbon 6 (DS6), is presented. It is shown that the direct-dissolution cellulose solvent, tetrabutylphosphonium acetate:DMSO-d6, converts 6-halo-6-deoxycelluloses to 6-monoacetylcellulose, enabling in situ solution-state NMR measurements. A range of 1D and 2D NMR experiments is used to demonstrate the quantitivity of the conversion and provide optimum dissolution conditions. In comparison with other NMR-based derivatization protocols for elucidating the structure of 6-halo-6-deoxycelluloses, the presented approach offers major advantages in terms of accuracy, speed, and simplicity of analysis, and minimal requirements for reagents or NMR instrumentation.

Gel characteristics of low-acetyl spruce galactoglucomannans.

Galactoglucomannans (GGM) recovered from abundant forest industry side-streams has been widely recognized as a renewable hydrocolloid. The low molar mass and presence of O-acetyl side-groups results in low viscous dispersions and weak intermolecular interactions that make GGM unsuitable for hydrogel formation, unless forcefully chemically derivatized and/or crosslinked with other polymers. Here we present the characterization of hydrogels prepared from GGM after tailoring the degree of acetylation by alkaline treatment during its recovery. Specifically, we investigated gel characteristics of low-acetyl GGM dispersions prepared at varied solid concentrations (5, 10 and 15 %) and pH (4, 7 and 10), and then subjected to ultrasonication. The results indicated that low-acetyl GGM dispersions formed gels (G' > G″) at all other studied solid concentration and pH level combinations except 5 % and pH 4. High pH levels, leading to further removal of acetyl groups, and high solid concentration facilitated the gel formation. GGM hydrogels were weak gels with strong shear-thinning behavior and thixotropic properties, and high hardness and water holding capacity; which were enhanced with increased pH and solid concentration, and prolonged storage time. Our study showed the possibility to utilize low-acetyl GGM as mildly processed gelling or thickening agents, and renewable materials for bio-based hydrogels.

Wood hemicelluloses as effective wall materials for spray-dried microcapsulation of polyunsaturated fatty acid-rich oils.

The most commonly-used and effective wall materials (WMs) for spray-dried microencapsulation of bioactive compounds are either costly, or derived from unsustainable sources, which lead to an increasing demand for alternatives derived from sustainable and natural sources, with low calories and low cost. Wood hemicelluloses obtained from by-products of forest industries appear to be attractive alternatives as they have been reported to have good emulsifying properties, low viscosity at high concentrations, high heat stability and low heat transfer. Here, we investigated the applicability of spruce galactoglucomannans (GGM) and birch glucuronoxylans (GX), to encapsulate flaxseed oil (FO, polyunsaturated fatty acid-rich plant based oil) by spray drying; and the results were compared to those of the highly effective WM, gum Arabic (GA). It was found that depending on solid ratios of WM:FO (1:1, 3:1 and 5:1), encapsulation efficiency of GGM was 88-96%, and GX was 63-98%. At the same encapsulation ratio, both GGM and GX had higher encapsulation efficiency than GA (49-92%) due to their ability to produce feed emulsions with a smaller oil droplet size and higher physical stability. In addition, the presence of phenolic residues in GGM and GX powders enabled them to have a greater ability to protect oil from oxidation during spray drying than GA. Physiochemical properties of encapsulated powders including thermal properties, morphology, molecular structure, particle size and water adsorption intake are also investigated. The study has explored a new value-added proposition for wood hemicelluloses which can be used as effective WMs in the production of microcapsules of polyunsaturated fatty acid-rich oils for healthy and functional products in food, pharmaceutical and cosmetic industries.

Spruce Galactoglucomannan-Stabilized Emulsions Enhance Bioaccessibility of Bioactive Compounds.

The increasing public awareness of health and sustainability has prompted the development of functional foods rich in health-promoting ingredients. Processing technologies and sustainable multifunctional ingredients are needed for structuring these formulations. Spruce galactoglucomannan (GGM), the main hemicelluloses in softwood cell walls, are an abundantly available, emerging sustainable food hydrocolloid that have the ability to efficiently emulsify and stabilize oil-in-water emulsions. In this study, we illustrate how this lignocellulosic stabilizer affects the digestion of polyunsaturated fatty acids (PUFAs) in vitro. A 100% decrease in the initial TAG content was observed during the in vitro digestion, suggesting that complete hydrolysis of the TAGs was achieved by the digestive enzymes. Besides, no release of mono-, di-, and oligosaccharides or phenolic compounds from GGM was detected. Our results demonstrate that the GGM-stabilized emulsion could potentially deliver lipophilic bioactive ingredients and enhance their bioaccessibility. In addition, this bio-stabilizer itself would remain stable in the upper gastrointestinal track and serve as a prebiotic for gut microbiota. We anticipate GGM to complement or even replace many of the conventional carriers of bioactive components in future health care products and functional foods.

Lignin-Rich PHWE Hemicellulose Extracts Responsible for Extended Emulsion Stabilization.

Wood hemicelluloses have an excellent capacity to form and stabilize oil-in-water emulsions. Galactoglucomannans (GGM) from spruce and glucuronoxylans (GX) from birch provide multifunctional protection against physical breakdown and lipid oxidation in emulsions. Phenolic residues, coextracted with hemicelluloses using the pressurized hot water (PHWE) process, seem to further enhance emulsion stability. According to hypothesis, phenolic residues associated with hemicelluloses deliver and anchor hemicelluloses at the emulsion interface. This study is the first to characterize the structure of the phenolic residues in both GGM- and GX-rich wood extracts and their role in the stabilization of emulsions. PHWE GGM and GX were fractionated by centrifugation to obtain concentrated phenolic residues as one fraction (GGM-phe and GX-phe) and partially purified hemicelluloses as the other fraction (GGM-pur and GX-pur). To evaluate the role of each fraction in terms of physical and oxidative stabilization, rapeseed oil-in-water emulsions were prepared using GGM, GX, GGM-pur, and GX-pur as stabilizers. Changes in droplet-size distribution and peroxide values were measured during a 3-month accelerated storage test. The results for fresh emulsions indicated that the phenolic-rich fractions in hemicelluloses take part in the formation of emulsions. Furthermore, results from the accelerated storage test indicated that phenolic structures improve the long-term physical stability of emulsions. According to measured peroxide values, all hemicelluloses examined inhibited lipid oxidation in emulsions, GX being the most effective. This indicates that phenolic residues associated with hemicelluloses act as antioxidants in emulsions. According to chemical characterization using complementary methods, the phenolic fractions, GGM-phe and GX-phe, were composed mainly of lignin. Furthermore, the total carbohydrate content of the phenolic fractions was clearly lower compared to the starting hemicelluloses GGM and GX, and the purified fractions GGM-pur and GX-pur. Apparently, the phenolic structures were enriched in the GGM-phe and GX-phe fractions, which was confirmed by NMR spectroscopy as well as by other characterization methods. The frequency of the main bonding pattern in lignins, the ß-O-4 structure, was clearly very high, suggesting that extracted lignin remains in native form. Furthermore, the lignin carbohydrate complex of γ-ester type was found, which could explain the excellent stabilizing properties of PHWE hemicelluloses in emulsions.